Process of treating hydrocarbon oils



1 Z r Z Nov. 10, 1936. R. B. PIERCE ET AL PROCESS OF TREATING HYDROCARBON OILS Filed Aug. 27, 1929 INVENTORS W ATTORNEY:

Patented Nov. 10, 1936 2,060,112

UNITED STATES PATENT OFFICE PROCESS OF TREigiiNG HYDROOARBON Ralph B. Pierce and Aubrey W. Trusty, Shreveport, La., assignors to Louisiana Oil Refining Corporation, Shreveport, La., a corporation of Virginia Application August 27, 1929, Serial No. 388,688

1 Claim. 196-28) This invention relates to the treatment of hyoften cannot be blended to produce a stable gasdrocarbon oils for the purpose of removing vaoline and will go badly off color. rious sulphur compounds therefrom and phrify- The following is a description of the equipment, ing the oil. The invention is applicable to and apparatus, design and method by which the incovers the conversion and removal or various vention may be carried out. It is to be under- 5 sulphur containing compounds, such as hydrostood, however, that the description is in no wise gen sulphide, mercaptans, monosulphides and dia limitation on other particular additions, sulphides, for example. The invention as stated changes or redesign which may be made to better is applicable to hydrocarbon oils in general and handle the process in question, but is only deis especially suitable for topped and cracked scribed as a mea s o clea y indicating the p 10 naphthas from high sulphur bearing petroleum ticular method employed to obtain the'desired crudes, shale oils and products produced from esults. the dry distillation of coal. The process may be carried out with an ar- The use of the old time sulphuric acid method rangement of app us in i s mewhat di- 16 for removing sulphur from oils is disadvantaasrammatlcally in the accomp y g drawing in geous in that large losses are incurred as well as which parts are shown in sectional elevation.

the removal of some of the valuable unsaturated In h r w r f enc h racter I indicates compounds. These and other disadvantages are a furnace that y be heated y m ans of fuel v r by th present invention, burners 2. The furnace is provided with a bridge go Th cracked naphthas t t by t process wall 3 over the edge of which the hot products of of the present invention become more stable un- Combustion P to a er 4 in which a heatder the action of sunlight than naphthas treated ing Coil 5 is located. by the sulphuric acid method. No neutral salts A p y nk 6 r th hydrocarbon oil to be or esters are formed to give rise to acid properties deslllphulized s located in Such a p on that within the body of the treated oil when it is sub- P 7 leads from t to a P p 8 from e out- 25 Jected to redistillation or to the action of sunlet of which a pipe 9 ds to the heating coil 5 light-h in the heating chamber 4.

The process can be carried out in such a way A flue l0 extends from the lower portion of the that completely sweetened material may be obchamber 4 into a rtically disposed as flue l tained that does not require further chemical from the upper P n of which an outlet It leads 30 tr t t, to a stack. The lower corner of the gas flue II The process can also be carried out in such a may be filled W h a fill 11 h as asbestos. r way that incompletely sweetened material is obexample, to aid in causing the hot a s to be aptained which will require only very small quantip p y s ibu d- A v v d ai in t pi as ties of chemicals for final sweetening. This is I4 may be vid d at the wer p rtion of the due to the fact that sulphur compounds present gas fl 80 that air y be admi d o 00 1 in an untreated oil or in an acid treated oil can temper the hot gases, if desired. he e l be decomposed or their chemical form so changed may be covered with heat insulating material I5. by this process with formation or libration of A tr a chamber or a t n ham r I6 is hydrogen sulphide that the resultant deleterious locate in th flue S0 that i Will be h e 40 compounds may be readily removed by present by the gases that enter t h the flue A and accepted methods of removal. inert carrier ll, such as steel wool, for example, is

In carrying out this invention the sulphur reprovid d in t am "5 as a pp t for e ducing material acts as a catalyst thereby enacatalyst that is used for treating the vapors of the bling extremely large amounts of oil to be treated hydrocarbon oil. Cadmium sulphide has been 45 with small amounts of the sulphur reducing mafound to be a suitable catalyst for the purpose of terial, thus reducing treating costs. The sulphur desulphurizing the hydrocarbon oils. The filler content of the hydrocarbon oil is reduced very or support for the catalyst is packed loosely in materially by this process from its original sulthe chamber l6 and is thoroughly impregnated phur content without the accompanying removal with the catalyst, so that the vapors come into 50 of valuable hydrocarbon constituents. intimate contact with the catalyst and channel- It has been found that topped naphthas and ing of the vapors through the chamber does not cracked naphthas treated by this process may be take place. A pipe l8 for the vapors leads from successfully blended to produce a stable gasoline the heating coil 5 into the bottom of the cham- 56 whereas the two naphthas after acid treatment ber I6 and an outlet I9 is provided at the top 01' the chamber I for the treated vapors. Thermometers or thermostats 20 may be provided at diflerent elevations in the annular space between the chamber II and flue II to indicate the temperature and similar temperature indicating devices 2| may be provided in the chamber I.

In operating the device the oil to be treated is pumped from the tank 8 through the heating coil 5 to vaporize the oil. The hot gases from the iurnace I, after heating the coil 5, pass through the flue ll into the flue I I and heat the chamber ll, the temperature being controlled, it necessary, by admitting the desired amount of air through the inlet pipe ll. The temperature in the chamber I may range from 250 F. to 700 F., the temperature from about 600 F. to 700 F. having been found so far to be most satisfactory. The oil vapors pass through the pipe l8 into the treating chamber 16 where they come into contact with the cadmium sulphide and the treated vapors pass through the outlet I 9 into a condenser (not shown). The condensates from the treated oil may be washed with a weak solution of sodium hydroxide to remove the hydrogen sulphide.

The treatment of hydrocarbon oils containing sulphur compounds, as described above, has been found to convert the malodorous and corrosive sulphur compounds to sweet and non-corrosive compounds with practically no loss of the oil and with very little, if any, effect upon the unsaturated compounds in the oil. In case the treated material is not completely sweetened, it can be more easily-and cheaply doctor sweetened than untreated oils and has none of the neutral alkyl esters that are found in oils which had been treated by sulphuric acid method. The oil is also very stable to sunlight, and in view of the fact that the valuable unsaturated compounds are not removed, the material appears to have better anti-knock value.

Cadmium sulphide appears to act as a catalyst and is especially useful for decomposing mercaptans, sulphides, and disulphides with the formation of hydrogen sulphide.

We claim:

The process oi. refining cracked petroleum naphtha to decompose organic sulphur compounds present therein without polymerizing or otherwise destroying a substantial proportion of the unsaturated hydrocarbons of the naphtha, which comprises passing the cracked naphtha in a confined stream through a heating zone in whicnthe naphtha is vaporized, passing the resulting vapors through a contact zone in intimate contact with a steel wool carrier material impregnated with a cadmium sulphide catalyst, maintaining a controlled temperature of from 600 to 700 F. in said contact zone, condensing the treated naphtha vapors from said contact zone, and washing the resulting condensate with an alkali solution to remove any hydrogen sulphide contained therein.

RALPH B. PIERCE. AUBREY W. TRUSTY. 

